Henby hebman stobch



P.......1- Aug. so, 1932 P UNITED STATES PATENT. OFFICE HENRY WB'I'OBUH, OF NEW YORK, N. Y ASSIGNOB, BY MESNE ASSIGNMENTS, TO m BOESIOER & HASSLAGHER OHBHIGAL COMPANY, A CORPORATION 01' DELA- arm cunts! r03. m m'rnnsrs or mmon llo Drawint.

I have discovered that copper in combination with calcium oxide forms an excellent catalyst fortltisreaction.

236 arts [Ga(N 41-1 0] and 100 parts by weight of copper nitrate [Cu(NO,) .3H O] were dissolved in' 1500 parts of water. To this solution was added while stirring a solution of 120 parts of sodium hydroxide in 500 parts of water. The precipitate was filtered out in a suction filter, washed free of nitrate and subsequently dried at about 150-200 G. This dried cake was then crushed to granules dried. material was about 36. CuO and p This mixture is now treated with reducing gases as will be describedbelow. The composition of the catalyst after this reduction treatment was approximately 31.9% Cu and 68.1% 0510. The'reduction can be carried v out by passing h drogen, or mixtures of hydrogen with car on monoxide or methanol or both over the heated mass. I prefer to reduce with hydrogen saturated at roo ntemperature with methanol. Inorder to prevent large uncontrollable increases in temperature during reduction it is usually desirable to and heated to not over 350 to about 150-200 C. The reduction is comlete when no further condensation of water is observed upon cooling the ofi-gases. .A

y weight of calciumnitrateof about 10-30 mesh. The com osition of the dilute the reducing gas with nitrogen or other Application fled August 9,1927. Serial 110. 210,210.

rough index of the progress of the reduction may be obtained by plotting the temperature .of the catalyst agalnst time. After the maximum temperature has been passed a further reduction period of about an hour. generally suflices to complete the reduction.

After this reduction treatment the granules were dark copper colored, and of a hard, firm I though-brittle structure suited for any methanol synthesis system. In this final form the catalyst is a mixture of copper and calcium oxide. c

In employing the catalyst for methanol synthesis from hydrogen and carbon monoxide it is desirable to use gasessubstantiall free from the common catalyst poisons whic may be present in the raw materials, such as, for example, arsenic, sulphur, phosphorus, volatile iron compounds, or other deleterious constituents gathered during the gas production.

The granular catalyst material was packed in a copper lined high pressure steel bomb and the whole heated to about 300 C. A gas mixture, comprising essentially 4 volumes hydrogen and one volume carbon monoxide, and essentially free of catalyst poisons was now passed through the heated catalyst under a pressure of about 200 atmospheres and at a space velocity per hour (S. V. H.) equivalent to about 20,000 cubic feet of gas per cubic footof catalyst per hour, calculated at normal temperature and pressure, (N. T. P.

0 C. and 1 atmosphere). During this reac,

tion the temperature of the catalyst mass was about 300-340 C. A sustained yield of methanol was obtained equivalent to a space time yield (S. T. Y.) of 1930 pounds of methanol er cubic foot of catalyst per 24 hours. T e products formed were recovered fromthe ofi-gases by cooling while still under pressure. The product was about 97% methanol. The catalyst retained its granular form after use in the above manner 1 or extended periods of time. The catalyst at the gas inlet'was about 300 C. and at the exit was about 340 C.; the outer shell of the bomb containing the catalyst was main! tainedv at a temperature of about-300 C.

A highly suitable method of utilizing this 10' For this purpose, I prefer to pulverize thedried material before reduction and then com press this powder into small compact masses of desired form, such as, for example, pills. I have obtained excellent results with ills about one-fourth inch irr diameter and a out one-ei hth inch thick. After com ression into pills the catalyst is reduced as be ore and into the catalyst bomb as in the case of the granular catal st. A From the a ove results it is evident that this catalyst has superior quantities entirely unexpected of a catalyst mixture containing an alkaline material such as calcium oxide. Various statements have been made in the prior art which would lead one to believe that alkaline material such as this would produce highly impure methanol instead of this, however, a product of great purity was obtained. I have found in the course of many experiments with this catalyst that the exact quantities, proportions, etc. given in the preferred Y examples'of catalyst manufacture may be varied, and my catalyst can still be obtained. I have found in general that these catalyst materials are valuable with proportions of copper running up to 50% by weight of the finely reduced catalyst mass. If the percent of metallic reduced copper is above this amount, I have found that the catalysts sinter very easily and lose their effectiveness as methanol catalysts. I therefore prefer to maintain a percentage of copper below 50% 1) weight. If the percentage of copper is less t an 5 or 10% b weight of the catalyst mass, I have found t at the rate of conversion is not satisfactory. I therefore, prefer to have at least 5% and preferably over 10% of the catalyst mass as metallic copper. I have found that in general approximately 25-30% by weight of metallic copper gives the best results. I furthermore, do not wish to be limited in the utilization of this catalyst to the preferred example of methanol manufacture which I have given by way of illustration. This catalyst is of high activity and hence will; operate over alarge range of varying conditions, all combinations of which need not be given. have used this catalyst under many conditions and find that wide limits of pressure and temperature are permissible. All the factors such as temperature, S. V. H., pressure, etc. maybe varied in order to secure various S. T. Y.s or percent conversions which may be desired because of mechanical and thermal control or for manufacturing economies. This catalyst has also given good results with gas-mixtures where the ratio of hydrogen to carbon monoxide was less as wellas greater than that given in m preferred example. --My catalyst will orm methanoh is then ready for use. The pills are packed from a gas mixture having any ratio of hydrogen to carbon. monoxide, but if the ratio is below one to one by volume the S. T. Y. will be considerably lower than that obtained with hydrogen in excess by volume." In general I prefer not to use less hydrogen than that required theoretically by the equation 2H CO CH OH I have found that a gas containin about four volumes of hydrogen to each v0 ume of carbon monoxide gives the best results, and

that with about 6 volumes of hydrogen the S. T. Y. is somewhat lower. reasons I, therefore, prefer 'not to exceed 6 volumes of hydrogen for each volume of carbon monoxide, but I do not wish to be limited For economic to this amount since methanol will be formed with the higher hydrogen ratios.

This catalyst is suited for the above syntheses at temperatures ranging between 150 C. and 450 C. althou h I have found but I do not wish to be limited to this range.

The catalyst will form methanol under the pressure and temperature limits given above at any space velocit Because of economic reasons, however, prefer space velocities of 2,000110 20,000 atN. T. P.

Claims: I

1. Process for the production of methanol which comprises passing a gaseous mixture ofhydrogen and carbon monoxide in contact with a hot catalyst mass comprising copper and calcium oxide.

2. Process for the production of methanol which comprises passing a gaseous mixture of hydrogen and carbon monoxide, containmg an excess of hydrogen at a pressure above atmospheric in contact with a hot catalyst mass comprising u to 50% by weight of reduced copper and t e Balance calcium oxide.

3. Process for the production of methanol which comprises passing a gaseous mixture of hydrogen and carbon monoxide containing an excess of hydrogen at a pressure of between 5 and 300 atmospheres in contact with a hot catalyst mass comprising copper and calcium oxide.

- 4. Process for the production of methanol which comprises passing a gaseous mixture of hydrogen and carbon monoxide containmg an excess of hydrogen at a pressure above atmospheric in contact with a catalyst mass comprising copper and calcium oxlde, said catalyst being maintained at a temperature of between 150 C. and 450 C.

5. Process for the production of methanol which comprises passing a gaseous mixture of hydrogen and carbon monoxide containing an excess of hydrogen at a pressure above atmospheric in contact with a catalyst mass- .10 comprising up to 50% reduced copper and the balance calcium oxide, said catalyst being maintained at a temperature of between 150 C. and 450 C. v

6. Process for the production of methanol which comprises passing a gaseous mixture of hydrogen and carbon monoxide containing an excessof hydrogen at a pressure of between 5 and 300 atmospheres in contact with a catalyst mass comprising copper and calcium oxide, said catalystbeing maintained at a temperature of between 150 C. and

7. Process for the production of methanol. which comprises passing a gaseous mixture of hydrogen and carbon monoxide containing an excess of hydrogen at a pressure of between 5 and 300 atmospheres in contact with a catalyst mass comprising copper and calcium oxide, said catalyst being maintained so at a temperature of between 300 and 400 C.

8. Process for the production of methanol which comprises passing a gaseous mixture of essentially four volumes of hydrogen and one volume of carbon monoxide at a pressure of between 5 and 300 atmospheres in contact with a catalyst mass comprising up to 50% reduced copper and the balance calcium oxide, said catalyst being maintained at a temperature of between 300 and 400 C.

Signed at Perth Amboy, in the county of Middlesex, and State of New Jersey, this 25th day of July, A. D. 1927. HENRY HERMAN ,STORCH. 

